JP2010100697A - Non-curable coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-curable coating composition using modified silicones each having a functional group, and capable of effectively preventing or suppressing the sticking of adhesive contaminants to a base material surface. <P>SOLUTION: The non-curable coating composition contains a carboxy modified silicone having a carboxy group in a side chain and an epoxy-oxyalkylene modified silicone having an epoxy group and an oxyalkylene group in side chains in a weight ratio of 1:2 to 1:30. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a non-curable coating composition used for avoiding adhesion of various adhesive substances to a substrate surface.

 Various coating agents are used to prevent adhesion of adhesive substances or contaminants to various substrates when molding and processing adhesive substances such as foods, adhesives, asphalt, tar, plastics, rubber, etc. Yes.

 For example, frozen food packaging materials; surface treatment agents for food cooking utensils such as frying pans and pan-bakers; mold release agents for molding plastics and rubber; paperboard containers used for cooling and solidifying asphalt, tar, etc. Various coating agents are used as release agents for preventing adhesion between substrates coated with an adhesive such as an inner surface treating agent; adhesive tape, pressure-sensitive adhesive tape, emblem. In addition, when recycling recycled paper to produce recycled paper, various adhesive components such as pitch, tar, and ink contained in the used paper are prevented from adhering to the press roll, dryer roll, canvas, etc. of the paper machine. The coating agent is also used for the purpose.

 Such a coating agent is applied to a substrate and then cured to form a non-adhesive layer, and applied to the substrate in a liquid state to form a non-adhesive layer, which is left as it is without being cured. There are non-curing types to use. The surface treatment agent, the inner surface treatment agent, and the release agent are curable, while the coating agent used in the recycled paper manufacturing process belongs to a non-curable type. As the mold release agent, both curable and non-curable types are known.

 For example, the following are known as non-curable coating agents.

 Japanese Laid-Open Patent Publication No. 4-130190 discloses a papermaking dryer surface cleaning lubricant comprising an oily substance and a surfactant. Examples of the oily substance include polybutene, machine oil, liquid paraffin, and the like. However, in order to form a non-adhesive layer made of these oily substances, a large amount of oily substances are required, which is an economic problem. Therefore, in Japanese Patent Laid-Open No. 7-292382, silicone oil made of polydimethylsiloxane is used to obtain a sufficient non-adhesive layer while reducing the amount of oily substance as much as possible.

 Silicone oil made from polydimethylsiloxane is oriented to the surface of the substrate with oxygen atoms of the siloxane main chain, and the silicon-bonded methyl groups to the outside. When applied to the base material, the non-adhesive layer made of the silicone oil will more strongly cover the surface of the base material. It may transfer to the paper body and the adhesive component in the used paper may adhere to the surface of the base material.

Therefore, it has been proposed to use a silicone oil having a functional group instead of the silicone oil made of polydimethylsiloxane. For example, Japanese Patent Application Laid-Open No. 2000-96476 proposes to apply various silicone oils to a canvas in a paper machine. As this silicone oil, in addition to methylphenyl silicone oil and diethylsilicone oil, amino-modified silicone is used. Examples include oils, epoxy-modified silicones, and higher fatty acid-modified silicone oils. Further, in Japanese Patent Application Laid-Open No. 2003-213587 (Patent No. 3388450), an oil-in-water (O / W) emulsion of an epoxy-modified silicone oil or an amino-modified silicone oil is sprayed on the surface of a dryer roll and canvas of a papermaking process. A method for preventing the adhesion of dirt on a dryer roll or a canvas surface by forming a non-adhesive layer has been proposed.
Japanese Patent Laid-Open No. 4-130190 JP 7-292382 A JP 2000-96476 A JP 2003-213587 A

 Certainly, when a modified silicone oil having a functional group rich in reactivity such as an epoxy group, an amino group, or a carboxy group is used as a coating agent for a substrate such as a press roll, a dryer roll, or a canvas of a paper machine, the modified silicone oil is used. Is more useful than silicone oil made of polydimethylsiloxane because of its high adhesion to the surface of the substrate. However, even if modified silicones having these functional groups are used, adhesion of adhesive components such as pitch to the substrate surface cannot be avoided sufficiently immediately.

  The present invention provides a non-curable coating composition that uses a modified silicone having a functional group and can effectively prevent or reduce adhesion of an adhesive substance to the surface of a substrate. Objective.

（式中、
Ｒは、それぞれ独立して、Ｃ_１−６アルキル基を表し；
Ａは、カルボキシ含有基を表し；
ｍは０〜１０００の整数を表し；
nは２〜１００の整数を表す）
で表されるカルボキシ変性シリコーン、及び、
下記一般式（２）：

（式中、
Ｒは、それぞれ独立して、Ｃ_１−６アルキル基を表し；
Ｘは、エポキシ含有基を表し；
Ｙは、オキシエチレン含有基を表し；
ｐは、０又は１を表し；
ｑは、０又は１を表し；
ｘは、０〜５００の整数を表し；
ｙは、１〜１００の整数を表し；
ｚは、１〜３００の整数を表す）
で表されるエポキシ・オキシアルキレン変性シリコーン
を１：２〜１：３０の重量比で含むことを特徴とする非硬化型コーティング用組成物によって達成される。 The object of the present invention is to provide the following general formula (1):

(Where
Each R independently represents a C _1-6 alkyl group;
A represents a carboxy-containing group;
m represents an integer of 0 to 1000;
n represents an integer of 2 to 100)
A carboxy-modified silicone represented by:
The following general formula (2):

(Where
Each R independently represents a C _1-6 alkyl group;
X represents an epoxy-containing group;
Y represents an oxyethylene-containing group;
p represents 0 or 1;
q represents 0 or 1;
x represents an integer of 0 to 500;
y represents an integer of 1 to 100;
z represents an integer of 1 to 300)
The epoxy-oxyalkylene-modified silicone represented by the formula (1) is contained in a weight ratio of 1: 2 to 1:30.

The carboxy-containing group is preferably represented by the formula: — (CH ₂ ) ₁ —COOZ (Z represents H, an alkali metal, or ammonium; l represents an integer of 0 to 12).

 The epoxy-containing group is preferably a glycidoxyalkyl group, an epoxycycloalkylalkyl group, or an oxiranylalkyl group.

The oxyethylene-containing group has the formula: — (CH ₂ ) _r — (OC ₂ H ₄ ) _s — (OC ₃ H ₆ ) _t —B (B is H, OH, OR, COOH or COOR (where R is And r represents an integer of 0 to 4, s represents an integer of 1 to 200, t represents an integer of 0 to less than 200, and 0 ≦ t <s). Is preferred.

 The weight ratio is preferably in the range of 1: 3 to 1:20.

 The non-curable coating composition of the present invention is preferably in the form of an oil-in-water or water-in-oil emulsion.

 The non-curable coating composition of the present invention can be used as a non-adhesive layer forming coating agent or a paper machine contamination inhibitor.

  The non-curable coating composition of the present invention can form a non-adhesive layer on the surface of a substrate, and can effectively prevent or reduce adhesion of an adhesive substance to the surface. The effect of the present invention is particularly brought about by the balance between the non-adhesive layer forming action due to the high adhesion to the substrate surface possessed by the carboxy-modified silicone and the adhesion preventing action of the adhesive substance possessed by the epoxy-oxyalkylene-modified silicone. Conceivable.

 The non-curable coating composition of the present invention can be used for various substrates as a non-curable coating agent. In particular, it can be applied to the surface of paper machine press rolls, dryer rolls, canvases, etc., and adhesion of adhesive contaminants such as pitch, tar, ink, etc. to the surface can be effectively avoided.

  The non-curable coating composition of the present invention does not have the property of being cured by heat or moisture, and on the contrary, does not need to be cured, and is a composition that can be coated as it is to exhibit the effects of the present invention, In addition, the carboxy-modified silicone having a carboxy group in the side chain and the epoxy-oxyalkylene-modified silicone having an epoxy group and an oxyalkylene group in the side chain are included in a specific ratio.

（式中、
Ｒは、それぞれ独立して、Ｃ_１−６アルキル基を表し；
Ａは、カルボキシ含有基を表し；
ｍは０〜１０００の整数、好ましくはｍ＋ｎが２〜１０００、より好ましくは３００〜１０００、特に好ましくは３８０〜５００の範囲に入るように選択された整数を表し；
nは２〜１００の整数、好ましくは２〜２０の整数を表す）
で表される。 The carboxy-modified silicone has the following general formula (1):

(Where
R each _{independently} represents a _{C 1-6} alkyl group;
A represents a carboxy-containing group;
m represents an integer of 0 to 1000, preferably m + n is 2 to 1000, more preferably 300 to 1000, particularly preferably 380 to 500;
n represents an integer of 2 to 100, preferably an integer of 2 to 20)
It is represented by

As the C _1-6 alkyl group, straight chain such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, etc. Or a branched alkyl group is mentioned. A methyl group is particularly preferable.

The carboxy-containing group has the formula: — (CH ₂ ) ₁ —COOZ (Z represents H, alkali metal or ammonium; l represents an integer of 0 to 12, preferably 0 or an integer of 3 to 11). Those represented are preferred. Examples of the alkali metal include sodium and potassium. X is preferably an alkali metal or ammonium in view of the stability of the composition.

  In addition to the type having a carboxy group at least in the side chain of the polysiloxane main chain (side chain type), the carboxy-modified silicone includes a type having a carboxy group only at both ends (both terminal types). Use side chain type. Since both terminal types have only two carboxy groups in one molecule, it is difficult to ensure adhesion to the substrate surface, and the amount used is larger than that of the side chain type, leading to the substrate surface. It becomes difficult to control the adhesion of the material. On the other hand, since the side chain type has a relatively large amount of carboxy groups, it is relatively easy to control the adhesion from the amount used.

Examples of the carboxy-modified silicone include (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _m [CH ₃ {HOOC (CH ₂ ) _{2 to 10} } SiO] _n Si (CH ₃ ) ₃ (m and n Is as described above, provided that m + n is in the range of 380 to 500).

（式中、
Ｒは、それぞれ独立して、Ｃ_１−６アルキル基を表し；
Ｘは、エポキシ含有基を表し；
Ｙは、オキシエチレン含有基を表し；
ｐは、０又は１を表し；
ｑは、０又は１を表し；
ｘは、０〜５００の整数、好ましくは０〜１２０の整数、より好ましくは３〜５０の整数を表し；
ｙは、１〜１００の整数、好ましくは１〜１０の整数、より好ましくは１〜５の整数を表し；
ｚは、１〜３００の整数、好ましくは１〜１０の整数、より好ましくは１〜５の整数を表す）
で表される。 The epoxy-oxyalkylene-modified silicone has the following general formula (2):

(Where
Each R independently represents a C _1-6 alkyl group;
X represents an epoxy-containing group;
Y represents an oxyethylene-containing group;
p represents 0 or 1;
q represents 0 or 1;
x represents an integer of 0 to 500, preferably an integer of 0 to 120, more preferably an integer of 3 to 50;
y represents an integer of 1 to 100, preferably an integer of 1 to 10, more preferably an integer of 1 to 5;
z represents an integer of 1 to 300, preferably an integer of 1 to 10, more preferably an integer of 1 to 5.
It is represented by

  The epoxy-containing group is necessarily present in the side chain of the polysiloxane main chain, but is not necessarily present at the terminal. The epoxy-containing group does not exist only at the end of the polysiloxane main chain. The epoxy-containing group is not particularly limited, but glycidoxyalkyl groups such as 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4-glycidoxybutyl group; 2- (3 An epoxycycloalkylalkyl group such as 4-epoxycyclohexyl) ethyl group and 3- (3,4-epoxycyclohexyl) propyl group; oxiranylmethyl group, 2-oxiranylethyl group, 4-oxiranylbutyl group, An oxiranylalkyl group such as an 8-oxiranyloctyl group is preferable, a glycidoxyalkyl group and an epoxycycloalkylalkyl group are more preferable, a 3-glycidoxypropyl group, and 2- (3,4-epoxycyclohexyl). An ethyl group is particularly preferred.

The oxyethylene-containing group has the formula: — (CH ₂ ) _r — (OC ₂ H ₄ ) _s — (OC ₃ H ₆ ) _t —B (B is H, OH, OR, COOH or COOR (where R is R represents an integer of 0 to 4, preferably an integer of 2 to 4, and s represents an integer of 1 to 200, preferably an integer of 5 to 100, more preferably an integer of 10 to 50. , T represents an integer of 0 to less than 200, preferably an integer of 0 to less than 100, more preferably an integer of 0 to less than 10 and 0 ≦ t <s). As is clear from the definition of this formula, the oxyethylene-containing group may contain an oxypropylene group, but when an oxypropylene group is present, the ratio of oxyethylene group / oxypropylene group may exceed 1. Moreover, it is more preferable that an oxypropylene group does not exist. Therefore, in the above formula, t = 0 is particularly preferable.

Examples of the epoxy-oxyalkylene-modified silicone include (CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) _{3 to 503} ((CH ₃ ) X′SiO) _{1 to 5} ((CH ₃ ) Y′SiO) during _1~5 Si (CH _{3) 3} formula, 'represents = .gamma.-glycidoxypropyl group, Y' X = - a (OCH ₂ CH ₂₎ represents an _{10~50 -OH) - (CH 2)} 3 Can be used.

  It is also conceivable to use a mixture of an epoxy-modified silicone oil and an oxyalkylene-modified silicone oil instead of the epoxy / oxyalkylene-modified silicone oil represented by the general formula (2). However, when the non-curable coating composition of the present invention is used in a paper machine, it has an affinity for wet paper having an oxyalkylene group and an anti-adhesion property to adhesive contaminant components such as paper and pitch having an epoxy group. It is more convenient to use an epoxy / oxyalkylene-modified silicone oil having both of the above in consideration of the adhesion preventing property to a press roll on a wet paper surface containing an adhesive component such as a pitch immediately after papermaking in an actual process.

  Further, when the non-curable coating composition of the present invention is used in a paper machine, the oxyalkylene moiety of the epoxy-oxyalkylene-modified silicone represented by the general formula (2) is composed of a polyoxyethylene group. However, it is preferable in terms of non-adhesion to the surface of the press roll, dryer roll, and canvas of a paper machine.

  The non-curable coating composition of the present invention can be produced by mixing the carboxy-modified silicone of the general formula (1) and the epoxy-oxyalkylene-modified silicone of the general formula (2) by a known method. The mixing ratio is from 1: 2 to 1:30 in a weight ratio of carboxy-modified silicone of general formula (1): epoxy-oxyalkylene-modified silicone of general formula (2). A range of 20 is more preferred.

  In the non-curable coating composition of the present invention, the carboxy-modified silicone represented by the general formula (1) and the epoxy-oxyalkylene-modified silicone represented by the general formula (2) are used in combination to adhere to the substrate surface. The mold release effect can be exhibited by the ability to form a non-adhesive layer due to the property and the ability to prevent adhesion to adhesive contaminant components such as pitch.

  The non-curable coating composition of the present invention may be used after being dissolved in an organic solvent. However, in order to reduce the burden on the environment, it may be in the form of an oil-in-water type or a water-in-oil type emulsion. preferable. In this case, water and an emulsifier may be added to the mixture of the carboxy-modified silicone of the general formula (1) and the epoxy / oxyalkylene-modified silicone of the general formula (2) to emulsify, but the carboxy-modified of the general formula (1) Water and an emulsifier can be added to each of the silicone and the epoxy-oxyalkylene-modified silicone of the general formula (2) and emulsified in advance, and then both can be mixed to form an emulsion-type non-curable coating composition. The emulsification method at this time can be performed by means / equipment that is normally performed.

  As an emulsifier for preparing the emulsion, any emulsifier used for preparing a silicone emulsion can be used, and any anionic, cationic, amphoteric or nonionic emulsifier can be used. An emulsifier may be used independently and may use two or more types together.

  Examples of the anionic surfactant include saturated or unsaturated higher fatty acid salts (for example, sodium stearate), long chain alkyl sulfates, alkylbenzene sulfonic acids (for example, dodecylbenzene sulfonic acid) and salts thereof, polyoxy Alkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyethylene alkyl sulfate ester salt, sulfosuccinic acid alkyl ester salt, polyoxyalkylene sulfosuccinate, long chain alkane sulfonate, polyoxyalkylene alkyl ether acetate, Long chain alkyl phosphate, polyoxyalkylene alkyl ether phosphate, acyl glutamate, alkyloyl alkyl taurine salt, N-acyl amino acid salt, alkyl alkyl ether carboxylate, α-sulfate E fatty acid ester salts, alanine derivatives, glycine derivatives, arginine derivatives. Examples of the salt include alkali metal salts such as sodium salts, alkanolamine salts such as triethanolamine salts, and ammonium salts, and sodium salts are preferable.

  Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts and dialkyldimethylammonium salts.

  Amphoteric surfactants include imidazoline type, amide betaine type, alkyl betaine type, alkyl amide betaine type, alkyl sulfobetaine type, amide sulfobetaine type, hydroxysulfobetaine type, carbobetaine type, phosphobetaine type, aminocarboxylic acid type An amide amino acid type amphoteric surfactant is exemplified.

  Examples of nonionic surfactants include polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, polyoxyalkylene resin acid esters, polyoxyalkylene alkylphenols. , Polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene glycerin fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, alkyl glucosides And polyoxyalkylene fatty acid bisphenyl ethers.

  Any additive may be added to the non-curable coating composition of the present invention as long as the purpose is not impaired. As said additive, a viscosity modifier, a pH adjuster, an antifoamer etc. are mentioned, for example. The type and amount of the additive can be appropriately adjusted according to the use of the non-curable coating composition of the present invention.

  The non-curable coating composition of the present invention can be used as a coating agent for various substrates. The coating agent of the present invention forms a non-adhesive layer on the substrate surface by being applied to the substrate surface. Thereby, adhesion of various substances to the substrate surface is prevented or reduced, and contamination of the substrate surface can be prevented. The coating amount of the coating agent on the substrate surface and the concentration of the non-curable coating composition in the coating agent can be appropriately changed depending on the type and size of the substrate.

  The non-curable coating composition of the present invention can be particularly suitably used as a stain preventer for paper machines.

  FIG. 1 is a schematic sectional view showing an example of a general drying process of a paper machine. In general, in the drying process, a web-like wet paper web W conveyed from a pressing process (not shown) is supplied between the heated dryer roll 1 and the rotating top canvas 7, and the pressure by the top canvas 7 is increased. Pressed against the surface of the dryer roll 1 to absorb the heat of the dryer roll 1. Next, the wet paper web W is separated from the surface of the dryer roll 1 by the rotation of the top canvas 7 and is supplied between the dryer roll 2 and the bottom canvas 8. Here, the wet paper web W is pressed against the surface of the dryer roll 2 by the pressure of the bottom canvas 8 and further absorbs the heat of the dryer roll 2. Then, the wet paper web W leaves the surface of the dryer roll 2 by the rotation of the bottom canvas 8 and is supplied between the top canvas 7 and the dryer roll 3, and the above steps are repeated. In this manner, the wet paper web W is sequentially pressed against the surfaces of the dryer rolls 1, 2, 3, 4, 5, 6 by the rotation of the top canvas 7 and the bottom canvas 8, and gradually absorbs the heat of each dryer roll. It will be dried.

  The wet paper web W contains various components such as pitch and tar contained in the pulp raw material itself, and ink contained in the used paper raw material. Since these components are often sticky, when the paper is made without applying any coating to the dryer rolls 1, 2, 3, 4, 5, 6 and the top canvas 7 and the bottom canvas 8, When the wet paper web W is pressed against the dryer rolls 1, 2, 3, 4, 5, 6, and the top canvas 7 and the bottom canvas 8, the components adhere to these surfaces and contaminate the surfaces. Since the wet paper web W adheres excessively to the contaminated dryer roll and canvas, and seizure and paper breakage occur, it is necessary to clean the dryer roll and canvas surface with a doctor blade or the like. However, since it is necessary to stop the paper machine to perform the cleaning operation, the production efficiency of the paper product is significantly reduced.

  Therefore, by applying the non-curable coating composition of the present invention to the surface of a dryer roll and / or canvas, a non-adhesive layer is formed on the surface to effectively prevent or reduce contamination. be able to. Specifically, the coating amount is adjusted to an emulsion containing 20% of the non-curable coating composition of the present invention, and is 0.1 to 50 cc / min, preferably 1 to 20 cc / min in terms of the coating solution. It is preferable to spray the non-curable coating composition so that

  In the example shown in FIG. 1, the non-curable coating composition is applied to the surfaces of the top canvas 7 and the bottom canvas 8 before contacting the wet paper web W by the spray S1 and the spray S2, respectively. Also, the non-curable coating composition is sprayed onto the surface of the dryer roll 1 by spray S3. The sprays S1, S2, and S3 may be fixed, or may be movable in the width direction of the canvas and dryer roll. It is preferable to spray-apply the non-curable coating composition on the surfaces of the dryer rolls 2, 3, 4, 5 and 6. However, if the composition is applied to the surface of the dryer roll 1, the dryer roll 1 is changed to the wet paper body W. Since the transferred part of the non-curable coating composition is transferred to the surfaces of the dryer rolls 2, 3, 4, 5, 6, it may be sprayed only on the surface of the dryer roll 1.

  Thus, by applying the non-curable coating composition of the present invention to the surfaces of a dryer roll and a canvas, it is possible to effectively prevent or reduce the adhesion of contaminants such as pitch, tar and ink to the surfaces. Therefore, the frequency of cleaning the surface can be reduced and the productivity of the paper product can be improved.

 Although FIG. 1 shows only the drying process of the paper machine, the non-curing type coating of the present invention is also used in the press process of producing a web-like wet paper body by pressing the wet paper with a press roller in the paper machine. A composition for use can also be used. In this case, the surface of the press roller can be prevented from being contaminated by applying the non-curable coating composition of the present invention to the surface of the press roller by spraying or the like. In this way, the non-curable coating composition of the present invention can be suitably used as a paper machine antifouling agent.

  The non-curable coating composition of the present invention can be used in a wide range of fields, for example, as a coating agent (for example, a release agent) for various substrates such as plastics and molds for molding rubber. In particular, the non-curable coating composition of the present invention is a paper machine for preventing or reducing the adhesion of contaminants such as pitch, tar, and ink to press rolls, dryer rolls, canvases and the like used in paper machines. It can be suitably used as an antifouling agent.

  EXAMPLES Hereinafter, although an Example and a comparative example illustrate this invention in detail, this invention is not limited to an Example. The functional silicone components used in the examples and comparative examples are as follows.

Carboxy oil A (side chain carboxy-modified silicone):

Carboxy oil B (both terminal carboxy-modified silicone):

Epoxy / polyether-modified silicone M (side-chain epoxy / polyoxyethylene-modified silicone):

X ′ = γ-glycidoxypropyl group
Y '=-(CH ₂ ) _3- (OCH ₂ CH ₂ ) ₁₂ -OH

Epoxy / polyether-modified silicone N (side-chain epoxy / polyoxypropylene-modified silicone):

X ′ = γ-glycidoxypropyl group
Y ”=-(CH ₂ ) _3- (OCH ₂ CH ₂ CH ₂ ) ₁₂ -OH

Epoxy-modified silicone:

X ′ = γ-glycidoxypropyl group

Polyether modified silicone:

Y '''= - (CH 2) 3 - (OCH 2 CH 2 O) 18 - (OCH 2 CH 2 CH 2) 18 -OH

Example 1
Carboxy oil A and epoxy / polyether-modified silicone M were added in a mixing ratio of 1: 7 (2 parts by weight: 14 parts by weight) to a container equipped with a propeller-type stirrer, and the mixture was stirred at 300 rpm for 5 minutes. Furthermore, 5 parts by weight of a nonionic emulsifier (polyoxyethylene alkylene ether) was blended, and after stirring at 300 rpm for 5 minutes, 78.94 parts by weight of water was added, and stirring was further continued for 60 minutes. Thereafter, 0.06 part by weight of a pH adjuster (sodium carboxylate) was blended while stirring at 300 rpm. After 3 minutes, a pale blue translucent emulsion was obtained.

(Example 1 ')
A blue-white translucent emulsion was obtained in the same manner as in Example 1 except that carboxy oil A and epoxy / polyether-modified silicone M were separately emulsified and mixed.

(Comparative Example 1)
Example 1 was repeated except that the epoxy / polyether-modified silicone M was replaced with the epoxy / polyether-modified silicone N to obtain a milky white emulsion.

(Comparative Example 2)
Example 1 was repeated except that the epoxy-polyether-modified silicone M was replaced with an epoxy-modified silicone to obtain a milky white emulsion.

(Comparative Example 3)
Example 1 was repeated except that carboxy oil A, epoxy-modified silicone and polyether-modified silicone were mixed at a ratio of 1: 3.5: 3.5 to obtain a milky white emulsion.

(Comparative Example 4)
Example 1 was repeated except that the epoxy-polyether-modified silicone M was replaced with a polyether-modified silicone to obtain a milky white emulsion.

(Comparative Example 5)
Example 1 was repeated except that the epoxy / polyether-modified silicone M was replaced with dimethylpolysiloxane (1000 cts) to obtain a milky white emulsion.

(Comparative Example 6)
Example 1 was repeated except that carboxy oil A was replaced with carboxy oil B to obtain a milky white emulsion.

(Comparative Example 7)
Example 1 was repeated except that carboxy oil A was replaced with carboxy oil B and epoxy / polyether-modified silicone M was replaced with epoxy / polyether-modified silicone N to obtain a milky white emulsion.

(Comparative Example 8)
Example 1 was repeated except that the epoxy-polyether-modified silicone M was replaced with carboxy oil A to obtain a milky white emulsion.

(Comparative Example 9)
Example 1 was repeated except that carboxy oil A and epoxy / polyether-modified silicone M were all replaced with carboxy oil B to obtain a milky white emulsion.

(Comparative Example 10)
Example 1 was repeated except that the carboxy oil A was replaced with an epoxy / polyether-modified silicone M to obtain a milky white emulsion.

(Comparative Example 11)
Example 1 was repeated except that the carboxy oil A and the epoxy / polyether-modified silicone M were all replaced with the epoxy / polyether-modified silicone N to obtain a milky white emulsion.

(Comparative Example 12)
Example 1 was repeated except that carboxy oil A and epoxy / polyether-modified silicone M were all replaced with epoxy-modified silicone to obtain a milky white emulsion.

(Comparative Example 13)
Example 1 was repeated except that the carboxy oil A and the epoxy / polyether-modified silicone M were all replaced with the polyether-modified silicone to obtain a milky white emulsion.

(Comparative Example 14)
Example 1 was repeated except that carboxy oil A and epoxy / polyether-modified silicone M were all replaced with polydimethylsiloxane (1000 cts) to obtain a milky white emulsion.

[Evaluation 1]
A stainless steel plate (150 mm × 50 mm) was prepared and heated to 100 ° C. Thereafter, about 0.06 g of the emulsion of Example 1, Example 1 ′ and Comparative Examples 1 to 14 was sprayed on one side of the heated stainless steel plate and uniformly applied with Kimwipe. Immediately after application, a commercially available cloth adhesive tape (No. 159, manufactured by Teraoka Seisakusho, width 50 mm, length 100 mm) was applied to the application surface while releasing the presser air with the palm of the hand. After leaving in an oven at 105 ° C. for 25 minutes, the cloth adhesive tape is peeled off with bare hands, and the lightness of the peeling at that time is as if it were in the following four stages:
1. Very light peeling, good peeled surface (very good)
2. Easily peeled and peeled surface is reusable (good)
3. Peeled but peeled face of the face is unusable (cannot be used)
4). Cannot be peeled off or cannot be reused even if forcibly peeled off (close contact)
It was evaluated with. As a control, the case where no emulsion was applied was also evaluated. The results are shown in Table 1.

  From the results in Table 1, the combination of carboxy oil A having a carboxy group in the side chain and epoxy / polyether-modified silicone M having an epoxy group and a polyoxyethylene group in the side chain exhibits good release properties and is practically used. It can be seen that a tolerable non-adhesive layer is formed on the substrate. On the other hand, examples using carboxy oil B having a carboxy group only at both ends and an epoxy / polyether-modified silicone N having an epoxy group and a polyoxypropylene group in the side chain are inferior in peelability and cannot be practically used. It can be seen that an adhesive layer is formed.

(Examples 2-9 and Comparative Examples 15-17)
A milky white emulsion was prepared by repeating Example 1 except that the blending ratio of carboxy oil A and epoxy / polyether-modified silicone M was changed as shown in Table 2 (in Table 2, the value in parentheses represents g). Obtained. The obtained emulsion was evaluated in the same manner as described above. The results are shown in Table 2.

  From the results shown in Table 2, when the mixing ratio (weight ratio) of the carboxy oil A and the epoxy / polyether-modified silicone M is in the range of 1: 2 to 1:30, good peelability is exhibited. : It is understood that the range of 20 is particularly excellent in peelability.

[Evaluation 2]
Using the paper machine having the drying process shown in FIG. 1, the effect of the emulsion of Example 1 was verified under the following papermaking conditions. The results are shown below.

(Paper making condition 1)
Papermaking varieties: White paperboard Basis weight: 300-550 g / m ²
Paper making width: 2000mm
Emulsion application place: dryer roll 1
Emulsion spray rate: 170 cc / min (liquid obtained by further diluting the blue-white translucent emulsion of Example 1 100 times with water)
Emulsion spraying addition method: 11 fixed spray nozzles Paper making speed: 700-1300 m / min Effect: Stain on the surface of the dryer roll was improved. Specifically, when the emulsion was not used, it was necessary to clean the surface of the dryer roll with a doctor blade three times a month. By using the emulsion of the present invention, the number of cleanings was reduced to once every two months. As a result, the number of operation interruptions has been significantly reduced, and the work efficiency has clearly improved.

(Paper making condition 2)
Papermaking varieties: Core core Nissan: 520t
Basis weight: 160-180 g / m ²
Paper making width: 4400mm
Emulsion application place: dryer roll 1
Emulsion spray rate: 5 cc / min (liquid obtained by further diluting the blue-white translucent emulsion of Example 1 four times with water)
Emulsion spraying method: One self-propelled spray nozzle Paper making speed: Max. 500 m / min Effect: Soil adherence with a lower additive amount than the polydimethylsiloxane oil-based emulsion used so far (the one used in Comparative Example 14) Prevention could be realized. Specifically, when using a polydimethylsiloxane-based emulsion, it was necessary to clean the dryer roll surface once a month with a doctor blade, but when using the emulsion of the present invention (with the same solid content), the cleaning work was half a year. It was unnecessary for a while. As a result, the number of operation interruptions has been significantly reduced, and the work efficiency has clearly improved. In addition, since the adhesive part between the paper and the dryer roll surface is almost eliminated and the influence on the paper quality is eliminated, the paper making speed can be increased.

(Paper making condition 3)
Papermaking varieties: liner paper basis weight: 180-200 g / m ²
Paper making width: 4000mm
Emulsion application location: canvas emulsion application rate: 800 cc / min (liquid obtained by further diluting the blue-white translucent emulsion of Example 1 100 times with water)
Emulsion spraying method: 16 fixed spray nozzles Paper making speed: 800-900 m / min Effect: Paper dust from emulsion of amino-modified silicone base (amino group-containing polydimethylsiloxane having an amino equivalent of 3800 and a viscosity of 1800 cps) which has been used conventionally As a result, adhesion of dirt such as pitch was extremely reduced, and drying efficiency and paper quality were improved. As a result, the paper making speed can be increased by 5%.

  The emulsion of the present invention is superior in preventing dirt adhesion on the dryer roll surface in the paper making process and preventing paper adhesion to the dryer roll surface, as compared with a general emulsion based on polydimethylsiloxane. Therefore, the emulsion of the present invention is useful as a contamination preventive agent for a paper machine that can prevent paper dust and pitch from adhering to the surface of a dryer roll and improve paper quality and paper productivity in the paper making process.

Schematic sectional view showing an example of a general drying process of a paper machine

Claims (8)

The following general formula (1):

(Where
Each R independently represents a C _1-6 alkyl group;
A represents a carboxy-containing group;
m represents an integer of 0 to 1000;
n represents an integer of 2 to 100)
A carboxy-modified silicone represented by:
The following general formula (2):

(Where
Each R independently represents a C _1-6 alkyl group;
X represents an epoxy-containing group;
Y represents an oxyethylene-containing group;
p represents 0 or 1;
q represents 0 or 1;
x represents an integer of 0 to 500;
y represents an integer of 1 to 100;
z represents an integer of 1 to 300)
An epoxy-oxyalkylene-modified silicone represented by the formula (1) is contained in a weight ratio of 1: 2 to 1:30. The non-curing according to claim 1, wherein the carboxy-containing group is represented by the formula: — (CH ₂ ) ₁ —COOZ (Z represents H, alkali metal or ammonium; l represents an integer of 0 to 12). Mold coating composition. The non-curable coating composition according to claim 1 or 2, wherein the epoxy-containing group is a glycidoxyalkyl group, an epoxycycloalkylalkyl group, or an oxiranylalkyl group. The oxyethylene-containing group has the formula: — (CH ₂ ) _r — (OC ₂ H ₄ ) _s — (OC ₃ H ₆ ) _t —B (B is H, OH, OR, COOH or COOR (R is And r represents an integer of 0 to 4, s represents an integer of 1 to 200, t represents an integer of 0 to less than 200, and 0 ≦ t <s). Item 4. The non-curable coating composition according to any one of Items 1 to 3. The non-curable coating composition according to any one of claims 1 to 4, wherein the weight ratio is 1: 3 to 1:20. The non-curable coating composition according to any one of claims 1 to 5, which is in an oil-in-water or water-in-oil emulsion form. A non-adhesive layer-forming coating agent comprising the non-curable coating composition according to claim 1. 7. A paper machine antifouling agent comprising the non-curable coating composition according to claim 1.

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